CN106268815A - A kind of loaded nano Co catalysts and application thereof - Google Patents
A kind of loaded nano Co catalysts and application thereof Download PDFInfo
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Abstract
A kind of loaded nano Co catalysts and application thereof, it is characterized in that, by on the basis of catalyst and in terms of cobalt element, in catalyst, nanometer cobalt content is 3～65 weight %, and the preparation method of described catalyst comprises the steps: that (1) prepares nanometer cobalt dispersion liquid；(2) in the nanometer cobalt dispersion liquid that step (1) obtains, it is passed through oxygen-containing gas, obtains a kind of nanometer cobalt dispersion liquid reacted with oxygen-containing gas；(3) the dispersion liquid dipping carrier obtained by step (2), drying obtains loaded nano Co catalysts.Compared with the loaded nano Co catalysts that prior art obtains, the catalyst that the present invention provides is applied in F-T synthesis, and its stability and catalytic performance are all greatly improved.
Description
Technical field
The present invention relates to a kind of supported cobalt catalysts and the application in Fischer-Tropsch synthesis thereof.
Background technology
Along with Global Oil resource is more and more rare, people's pay attention to day by day to environmental conservation, utilize coal and sky
So gas etc. are increasingly subject to people's attention for raw material preparation cleaning fuels and chemicals.F-T synthesis technology is
One of key technology of these coals and natural gas clean utilization.
The primary product of the Fischer-Tropsch synthesis that synthesis gas changes into hydro carbons on a catalyst includes alkane and alkene
Hydrocarbon, product can get high-quality liquid fuel and chemicals through deep processing.
At present, load type cobalt-base catalyst is a kind of fischer-tropsch synthetic catalyst with industrial application value.One
As load type cobalt-base catalyst use infusion process to prepare, active component cobalt particle size is relatively big, and distribution is wide, cobalt
Utilization rate low and deactivation phenomenom is obvious.Additionally, in order to make cobalt oxide fully be reduced into the metallic cobalt of activity,
Generally using noble metal auxiliary agent, this results in significantly improving of catalyst cost.Therefore, how to improve
The utilization rate of cobalt, the utilization of minimizing noble metal, the stability improving catalyst and catalytic performance are the most all
It is difficult point and the direction of cobalt-base catalyst exploitation.
CN102274726 discloses a kind of activation method preparing supported cobalt catalysts.First prepare granule chi
Very little 3～20nm the cobaltosic oxide nano granule comprising auxiliary agent, then load on carrier, finally lead to
Cross hydrogen reducing.Catalyst activity prepared by the relatively conventional infusion process of this catalyst is doubled, but selects
Property does not has significant change.
Kou Yuan et al. (catalysis journal, the 2013, the 10th phase, 1914～1925) discloses and exists at protective agent
Under, the method reduced by control prepares the method for aqueous phase Co nano-particle, although low temperature active is higher,
But granule stability is poor.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high activity, high selectivity and the catalysis of high stability
Agent, and the application in F-T synthesis of this catalyst is provided.
In order to realize above-mentioned technical purpose, the present invention provides following technical scheme, and particular content includes:
A kind of loaded nano Co catalysts, it is characterised in that by the basis of catalyst and in terms of cobalt element,
In catalyst, nanometer cobalt content is 3～65 weight %, and the preparation method of described catalyst comprises the steps: (1)
Prepare nano cobalt granule, the nano cobalt granule obtained is scattered in solvent, obtain nanometer cobalt dispersion liquid；(2)
In the nanometer cobalt dispersion liquid that step (1) obtains, it is passed through oxygen-containing gas, obtains one and react with oxygen-containing gas
Nanometer cobalt dispersion liquid；(3) with step (2) obtain dispersion liquid dipping carrier, drying is loaded
Type nanometer cobalt catalyst；Wherein, the operating condition of step (2) including: temperature is-10～60 DEG C, oxygenous
The volume space velocity of body is 0.2～20L g-1·h-1, the time is 0.01～24h.
According to the catalyst of the present invention, the particle diameter of the nano cobalt granule described in step (1) is 1～20nm,
Being preferably 3～15nm, in nanometer cobalt dispersion liquid, cobalt content is calculated as 1～10g cobalt/100mL solvent with cobalt element,
Being preferably 1～5g cobalt/100mL solvent, described solvent is selected from water, methanol, ethanol, propanol, acetic acid, breast
In acid, citric acid, PEG (Polyethylene Glycol, lower same), PVP (polyvinylpyrrolidone, lower same) one
Plant or several, preferably one or more in water, methanol, ethanol, propanol, acetic acid.Wherein said
Water can be distilled water, deionized water etc..
The catalyst provided according to the present invention, by the basis of catalyst and in terms of cobalt element, in catalyst, cobalt contains
Amount is preferably 5 weight %～50 weight %, and the particle diameter of nanometer cobalt is 1～20nm, preferably 3～15nm.
According to the present invention, in described step (2), operating condition is preferably: temperature 0～50 DEG C, and the time is 0.1～4h,
On the basis of nanometer cobalt quality, the volume space velocity of oxygen-containing gas is 1～10L g-1·h-1；Described in step (2)
Oxygen-containing gas is oxygen and the gaseous mixture of one or more in nitrogen, noble gas, in mixed gas
Oxygen content is not more than 21 volume %, preferably 0.01～5 volume %.
According to the present invention, the nanometer cobalt described in step (1) is metallic cobalt, can use any prior art system
Standby nano cobalt granule, such as, uses control reducing process (controlled reduction) to prepare, is included in guarantor
In the presence of protecting agent, use reducing agent that cobalt salt is carried out reduction reaction and obtain.Selectively, described control reduces
The process preparing nano cobalt granule is carried out in the presence of reaction medium, and in the presence of responding medium, reaction is situated between
Matter is one or more in water, methanol, ethanol, propanol, acetic acid, lactic acid, oxolane, citric acid,
It is preferably water, ethanol, oxolane or its mixture.Wherein said water can be distilled water, go from
Sub-water etc..Particularly as follows: cobalt salt and protective agent are joined, reaction medium obtains cobalt salt and protectant mixing
Solution, then joins reducing agent in mixed solution and reacts, obtain described nano cobalt granule.Described
The condition controlling reduction reaction includes: reaction temperature is-10～70 DEG C, and the response time is 0.01～4h；Reaction bar
Part preferably reaction temperature is 0～40 DEG C, and the response time is 0.1～2h.Described cobalt salt be cobalt inorganic salt or
Carboxylate, one or more in sodium borohydride, potassium borohydride, hydrazine hydrate of described reducing agent, institute
The ratio stating the reducing agent amount with element cobalt material is 3～20:1, preferably 3～15:1；Described protective agent
The material of one or more in PEG, PVP, oleic acid, linoleic acid, described protective agent and element cobalt
The ratio of amount be 10～500:1, preferably 20～200:1, when described protective agent is polymer, protection
The amount of the material of agent is in terms of monomer.
It is known to those skilled in the art about the method that be enough to make reduction reaction carry out under oxygen-free environment,
Such as: reaction is carried out under nitrogen storage condition or in the glove box of inert gas shielding, does not repeats.
The catalyst provided according to the present invention, wherein said carrier is the porous being commonly used for catalyst carrier
Heat-resistant inorganic oxide, such as, selected from aluminium oxide, titanium oxide, magnesium oxide, alumina-silica magnesium, oxidation
Silicon-aluminium oxide, silica-magnesias, silica-zirconia, silica thoria, silica-berylias,
Silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, oxygen
SiClx-aluminium oxide-titanium oxide, silicaalumina-magnesia, silica-alumina, zirconia, natural boiling
One or more in stone, clay.The specific surface area of carrier is 5～600 meters2/ gram, specific surface area is preferably
5～500 meters2/ gram, specific surface area more preferably 10～500 meters2/ gram.
The dipping of step of the present invention (3) refers to the described nanometer cobalt dispersion liquid reacted with oxygen-containing gas
Contact with carrier, and described nano cobalt granule is carried on the process on described carrier, realize this being enough to
On the premise of purpose, the method for described dipping is not particularly limited by the present invention, such as, by described dispersion liquid
The dipping method mixed with carrier.
In the present invention, described dipping complete after be dried to remove the solvent in described nanometer cobalt dispersion liquid as mesh
, on the basis of being enough to realize this purpose, described dry method is not particularly limited by the present invention, example
As used the method for evacuation to be dried, or the method using evacuation to combine heating is dried,
Or the method for heating is dried.
In a specific embodiment, the nano cobalt granule in described step (1) uses and controls reducing process
Preparation, including: in the presence of protective agent, use reducing agent that cobalt salt is carried out reduction treatment and obtain.Described
Cobalt salt is inorganic salt or the carboxylate of cobalt, can be selected from cobaltous chloride, cobalt nitrate, cobaltous sulfate, cobaltous formate, second
One or more in acid cobalt, cobalt oxalate, cobalt benzoate, described reducing agent is for reducing cobalt salt at normal temperatures
Generate the material of metallic cobalt, such as sodium borohydride, potassium borohydride, hydrazine hydrate etc., described protective agent selected from PVP,
One or more in PEG, oleic acid, linoleic acid.The reaction medium controlling reduction reaction can be water, first
One or more in alcohol, ethanol, propanol, acetic acid, lactic acid, citric acid, preferably water and ethanol or its
Mixture, more preferably water.Wherein said water can be distilled water, deionized water etc..Reaction
Preferably carrying out at 0～40 DEG C, the response time is preferably 0.1～2h, wherein the amount of reducing agent and the material of cobalt it
Ratio is 3～20:1, preferably 3～15:1；Protective agent is 10～500:1 with the ratio of the amount of the material of cobalt, excellent
Electing 20～200:1 as, when described protective agent is polymer, the amount of protectant material is in terms of monomer.For
Make the reaction preferably carry out, in controlling reduction process, system can blanketing with inert gas, as described also
Former carry out in glove box, glove box is filled with High Purity Nitrogen or high-purity argon gas.In the present invention, preferably include
The step washing the nano cobalt granule prepared, described washing makes in the nano cobalt granule obtained
On the basis of nano cobalt granule weight, other metal impurities gross weight content in addition to cobalt is not more than
100ppm.On the premise of reaching washing requirement, washing methods is not limited by the present invention, the most permissible
Use centrifuge washing, be i.e. centrifuged reaction system separating, in the solid matter obtained, add solvent wash
Washing, then recentrifuge separates, and as above operation can be repeated, and cleaning solvent can be water, ethanol
Or its mixture etc..Wash complete after, by nano cobalt granule dispersion obtain nanometer cobalt dispersion liquid in a solvent,
Described solvent can be water, methanol, ethanol, propanol, acetic acid, lactic acid, citric acid, Polyethylene Glycol, gather
One or more in vinylpyrrolidone, preferably water, methanol, ethanol, propanol, acetic acid, further
It is preferably ethanol.Wherein said water can be distilled water, deionized water etc..In the present invention, described in receive
Rice cobalt dispersion liquid is a kind of stable nanometer cobalt colloidal sol.In order to make nanometer cobalt dispersion liquid more stable and uniform
It is dispersed in disperse medium, ultrasonic means can be used to disperse.In the nanometer cobalt dispersion liquid obtained, with
TEM characterizes, and the particle diameter of described nano cobalt granule is 1～20nm, preferably 3～15nm.
Oxygen-containing gas is passed through in nanometer cobalt dispersion liquid in (2) by described step, makes oxygen and nano cobalt granule enter
Row effect, obtains a kind of nanometer cobalt dispersion liquid reacted with oxygen-containing gas, and this step can also be described as adopting
With oxygen-containing gas, nanometer cobalt is passivated the step processed.Except oxygen in the described mixed gas containing oxygen
Outside gas, other component can be selected from one or more in nitrogen, noble gas, in described oxygen-containing gas
Oxygen content is not more than 21 volume %, preferably 0.01～5 volume %；On the basis of nanometer cobalt quality, mixing
It is 0.2～20L/ (g h) that gas is passed through the volume space velocity of nanometer cobalt dispersion liquid, and duration of ventilation is 0.1～24h；Preferably
Under the conditions of, on the basis of nanometer cobalt quality, mixed gas is passed through the volume space velocity of nanometer cobalt dispersion liquid and is
1～10L/ (g h), duration of ventilation is for for 0.1～4h.
Carrier in described step (3) can make the various shape meeting requirement, such as depending on different requirements
Microsphere, spherical, tablet or bar shaped etc..Molding can be carried out according to a conventional method, such as, when required shaping carrier
When being shaped as the microsphere that can meet slurry bed system needs, described porous heat-resistant inorganic oxide article shaped can
With by preparing its precursor (such as, the precursor boehmite of aluminium oxide), afterwards, by this predecessor
Thing is spray-dried and prepared by the method for roasting.Can also be by buying the described many of commercially available met requirement
Precursor powder body (such as, the precursor of the spray-dried aluminium oxide obtained of permeability heat-resistant inorganic oxide
Boehmite powder body) and the method for roasting prepare.The method of described roasting and condition carry for preparing catalyst
The method of the roasting that body is usual and condition.Such as, the method for described roasting is roasting in air atmosphere
Method, wherein, the condition of described roasting includes: sintering temperature is 300～900 DEG C, preferably
350～850 DEG C, more preferably 550～800 DEG C, roasting time is 0.5～12 hour, and preferably 1～8 is little
Time, more preferably 2～6 hours.It is said that in general, on the premise of meeting slurry reactor requirement, this
Invent the particle diameter to described microsphere article shaped to be not particularly limited, in the preferred case, putting down of described article shaped
All particle diameters are preferably 20～150 microns, and wherein, the grain volume fraction less than 20 microns is not more than 5%,
The mean diameter of the most described article shaped is 30～120 microns, more preferably 40～100 microns.Wherein,
The evaluation particle diameter of described carrier uses ISO13320-1 grain size analysis-laser diffraction method to measure.
On the premise of being enough to realize on by described nanometer cobalt load carriers, the present invention side to described dipping
Method is not particularly limited, such as, and the dipping method that described dispersion liquid is mixed with carrier.In order to make nanometer cobalt
More stable and the uniform dispersion of dispersion liquid preferably having an effect with carrier, preferably described in be immersed in ultrasonic
Under the conditions of carry out.
Carrier after dipping is dried for the purpose of removing the solvent in described nanometer cobalt dispersion liquid,
On the basis of being enough to realize this purpose, described dry method is not particularly limited by the present invention, for example with
The method of evacuation is dried, or the method using evacuation to combine heating is dried, and rotates and steams
Send out instrument to be dried, or the method for heating is dried.
Present invention also offers the application in F-T synthesis of the described catalyst, be specifically included in F-T synthesis anti-
Under the conditions of Ying, by the mixture of carbon monoxide and hydrogen and described catalyst haptoreaction, described reaction condition
For: temperature is 160～300 DEG C, and pressure is preferably 1～8MPa, and the mol ratio of hydrogen and carbon monoxide is
0.4～2.5:1, the volume space velocity of gas is 200～40000h-1；Reaction condition is preferably temperature 190～280 DEG C,
Pressure 1～5MPa, the mol ratio 1.0～2.5:1 of hydrogen and carbon monoxide, the volume space velocity of gas is
500～30000h-1。
There is provided catalyst according to the present invention, preferably deposited at hydrogen-containing gas before using it for Fischer-Tropsch synthesis
Carry out reduction activation under, in noble gas can be contained in described hydrogen-containing gas in addition to the hydrogen
Plant or several, when described hydrogen-containing gas is hydrogen and the mixed gas of one or more in noble gas
Time, in mixed gas, hydrogen content is not less than 10 volume %, preferably not less than 20 volume %.Reduction is lived
The condition changed is: temperature is 100～800 DEG C, and the time is 0.5～72h, and pressure is 0.1～4MPa, gaseous mixture
Body volume space velocity is 200～50000h-1；Preferably reduction activation condition is: temperature 200～600 DEG C, enters one
Step is preferably 250～450 DEG C, and the time is 1～24h, and pressure is 0.1～3MPa, and mixed gas volume space velocity is
4000～40000h-1。
Compared with prior art, the catalyst that the present invention provides is applied in Fischer-Tropsch synthesis greatly to carry
The stability of high catalyst and catalysis activity.
Detailed description of the invention
The present invention is described further for the following examples.
In nanometer cobalt dispersion liquid and catalyst, the particle diameter of nanometer cobalt can pass through transmission electron microscope (TEM) acquisition, example
As, using FEI Co.'s FEI TECNAI G2 F20 S-TWIN type transmission electron microscope, voltage is
200kV, each sample is clapped under the conditions of 500,000～1,000,000 enlargement ratios and is taken 10-15 and open photo, from being taken pictures
Choosing more than 200 granules in sheet uses Nano Measure software to carry out grain diameter measurement, and to measurement result
Add up, obtain nano cobalt granule particle size data in nanometer cobalt dispersion liquid and catalyst.
Catalyst preparation process is all carried out in nitrogen atmosphere glove box.
Embodiment 1
(1) prepared by nanometer cobalt dispersion liquid: in the glove box under High Purity Nitrogen is protected, to the there-necked flask of band stirring
Middle addition 210ml distilled water, 15.4g protective agent PVP-30k (traditional Chinese medicines group, analytical pure) and 3.5g tetra-
Acetate hydrate cobalt (lark prestige, analytical pure), keeps 15 minutes under normal temperature condition, after slowly dissolving to solid,
Use syringe will contain the aqueous solution 30.8g fast injection of 2.8g sodium borohydride (Beijing reagent, analytical pure)
In there-necked flask, after continuing to react 15 minutes under the conditions of stirring at normal temperature, reactant liquor is transferred to centrifuge tube and enters
Row high speed centrifugation separates, and then is centrifuged washing 6 times to nano cobalt granule with distilled water, each consumption
50mL, obtains nano cobalt granule.Use ICP/AES method (RIPP 127-90) measure wherein except cobalt with
The weight content that other metal is total outward is less than 100ppm.Finally the nano cobalt granule obtained is dispersed in 30mL
Dehydrated alcohol obtains nanometer cobalt dispersion liquid.TEM record nano cobalt granule size integrated distribution in
4-6nm。
(2) Passivation Treatment: under agitation, is passed through above-mentioned cobalt metallic particles by the mixed gas of oxygen and nitrogen
In dispersion liquid, the flow of 3L/h keeps 1h, and in mixed gas, oxygen content is 0.1 volume %.
(3) load: the nano cobalt granule dispersion liquid after above-mentioned passivation is added 5.9g under the conditions of ultrasonic disperse
Aluminum oxide micro-sphere (Sasol Products, mean diameter 65 microns, specific surface area 180 meters2/ gram), mixing
After Jun Yun, utilize Rotary Evaporators to remove excess of solvent under 50 DEG C of condition of water bath heating, obtain support type and receive
Rice Co catalysts, is designated as C-1, and catalyst characterization data are shown in Table 1.
Comparative example 1
Compared with Example 1, the difference is that only and be not passivated process step, the catalyst obtained
Being designated as R-1, catalyst characterization data are shown in Table 1.
Comparative example 2
The method provided according to CN102274726, the preparation support type containing cobalt content same as in Example 1 is urged
Agent.Particularly as follows: by molten with the sodium carbonate that 30mL strong aqua ammonia, 3mL concentration are 1M for 45mL ethylene glycol
Liquid and the cobalt nitrate solution that 14mL concentration is 1M are anti-at 160 DEG C in proceeding to hydrothermal reaction kettle after mixing according to this
Answer 16h, be then washed with deionized solid product 3 times, washing with alcohol 2 times.Solid product adds 25mL
After 1M glucose solution and the mixing of 100mL deionized water, it is transferred to 180 DEG C of reactions in 300mL reactor
4h, solid sample is washed with deionized 6 times, washing with alcohol 1 time, then in argon gas atmosphere 700 DEG C
Process 200min, then in 250 DEG C of air, process 200min, obtain nano cobalt granule.Use ICP/AES
Method (RIPP 127-90) measures the weight content that other metal is total the most in addition to cobalt and is less than 100ppm.
Take above-mentioned nano cobalt granule 1.0g to be scattered in 30mL ethanol, after ultrasonic disperse, add 5.9g aluminium oxide
Microsphere (Sasol Products, mean diameter 65 microns, specific surface area 180 meters2/ gram), after mix homogeneously,
Utilize Rotary Evaporators to remove solvent under 50 DEG C of condition of water bath heating, obtain catalyst, be designated as R-2, urge
Agent characterizes data and is shown in Table 1.
Embodiment 2
Compared with Example 1, the difference is that only that in passivation step, Passivation Treatment condition is different, the most blunt
Change condition is: under static conditions, the mixed gas of oxygen and nitrogen is divided containing being passed through above-mentioned cobalt metallic particles
Dissipating in liquid, the flow of 0.2L/h keeps 30min, and in mixed gas, oxygen content is 5 volume %.Obtain institute
The loaded nano Co catalysts stated, is designated as C-2, and catalyst characterization data are shown in Table 1.
Embodiment 3
(1) prepared by cobalt nano-particle: under High Purity Nitrogen is protected, and adds 210ml in the there-necked flask with stirring
Distilled water, 24.6g protective agent PEG-20000 (traditional Chinese medicines group, analytical pure) and 5.2g Cobaltous oxalate,tetrahydrate
(lark prestige, analytical pure), treats that solid slowly dissolves, and stablizes 15 minutes under the conditions of ice-water bath, uses note
Emitter will contain the aqueous solution 32.8g fast injection to three mouthfuls of 4.8g potassium borohydride (Beijing reagent, analytical pure)
In Ping, after continuing reaction 30 minutes, reactant liquor is transferred to centrifuge tube and carries out high speed centrifugation separation, then use
Nano cobalt granule is centrifuged washing 6 times by distilled water, each consumption 50mL, obtains nano cobalt granule.
ICP/AES method (RIPP 127-90) is used to measure the weight content that other metal is total the most in addition to cobalt low
In 100ppm.Finally the nano cobalt granule obtained is dispersed in 30mL dehydrated alcohol and obtains nanometer cobalt dispersion
Liquid.TEM records nano cobalt granule size integrated distribution in 6-8nm.
(2) Passivation Treatment: under static conditions, is passed through above-mentioned cobalt metal by the mixed gas of oxygen and nitrogen
In grain dispersion liquid, the flow of 1L/h keeps 4h, and in mixed gas, oxygen content is 0.4 volume %.
(3) load: 4.3g oxygen will be added after metallic cobalt nanoparticulate dispersion ultrasonic disperse after above-mentioned passivation
SiClx microsphere (particle diameter 70～150 microns, specific surface area 250 meters2/ gram), 100 DEG C of vacuum drying oven is dried
24h obtains loaded nano Co catalysts after removing solvent, is designated as C-3, and catalyst characterization data are shown in Table 1.
Embodiment 4
(1) prepared by cobalt nano-particle: under High Purity Nitrogen is protected, and adds 610ml in the there-necked flask with stirring
Distilled water, 104.0g protective agent PEG-6000 (traditional Chinese medicines group, analytical pure) and 5.65g cobalt chloride hexahydrate
(lark prestige, analytical pure), treats that solid slowly dissolves, and stablizes 15 minutes under the conditions of ice-water bath, uses note
Emitter will contain the aqueous solution 32g fast injection of 20g hydrazine hydrate (Beijing reagent, content 50%, analytical pure)
In there-necked flask, after continuing reaction 30 minutes, reactant liquor is transferred to centrifuge tube and carries out high speed centrifugation separation,
Then it is centrifuged washing 6 times to nano cobalt granule with distilled water, each consumption 50mL, obtains nanometer cobalt
Granule.ICP/AES method (RIPP 127-90) is used to measure the weight that other metal is total the most in addition to cobalt
Content is less than 100ppm.Finally the nano cobalt granule obtained is dispersed in 30mL dehydrated alcohol and obtains nanometer
Cobalt dispersion liquid.TEM records nano cobalt granule size integrated distribution in 10-15nm.
(2) Passivation Treatment: under static conditions, is passed through above-mentioned cobalt metal by the mixed gas of oxygen and nitrogen
In grain dispersion liquid, the flow of 5L/h keeps 1h, and in mixed gas, oxygen content is 0.5 volume %.
(3) load: 2.0g oxygen will be added after metallic cobalt nanoparticulate dispersion ultrasonic disperse after above-mentioned passivation
SiClx-aluminum oxide micro-sphere (particle diameter 70～150 microns, specific surface area 250 meters2/ gram), 100 DEG C of vacuum drying oven
Being dried after 24h removes solvent and obtain loaded nano Co catalysts, be designated as C-4, catalyst characterization data are shown in
Table 1.
Table 1 catalyst property characterizes
Activation of catalyst and performance evaluation
Embodiment 5
Activation of catalyst is carried out in fixed bed or fluidized-bed reactor, weighs 8.6g catalyst and puts into activation instead
In answering device, preferred gas composition, air speed and at a temperature of keep certain time, be then cooled to room temperature,
Catalyst is proceeded in glove box, under oxygen-free environment add containing the rebasing oil of 150g (polyalphaolefin, Mobil,
In reactor 4#).
Wherein, each activation of catalyst condition is as follows:
C-1, C-2, R-1 and R-2 in 0.2MPa, 400 DEG C, mix in hydrogen argon mixed gas atmosphere
Close gas volume air speed 30000h-1Under the conditions of reduction activation 4h, wherein, in mixed gas, hydrogen content is 30
Volume %.
C-2 in hydrogen argon mixed gas atmosphere in 2.0MPa, 350 DEG C, mixed gas air speed 30000h-1
Under the conditions of reduction activation 4h, wherein, in mixed gas, hydrogen content is 70 volume %, after reduction activation
Catalyst is designated as C-2'.
C-3 in hydrogen argon mixed gas atmosphere in 2.0MPa, 350 DEG C, mixed gas air speed 30000h-1
Under the conditions of reduction activation 3h, wherein, in mixed gas, hydrogen content is 40 volume %.
C-4 in hydrogen argon mixed gas atmosphere in 1.0MPa, 380 DEG C, mixed gas air speed 20000h-1
Under the conditions of reduction activation 2h, wherein, in mixed gas, hydrogen content is 70 volume %.
Performance evaluation is carried out in continuous mixing still, and catalyst amount is shown in specific embodiment.Concrete operations bag
Include: will take out from glove box containing the autoclave of catalyst, rebasing oil, and load onto reactor and be ready for performance and comment
Valency, is first passed through nitrogen and carries out replacing and checking air-tightness.Under flowing nitrogen, it is warming up to 110 DEG C, then is passed through
Synthesis gas also continues to heat up, and synthesis gas consists of: H2:CO:N2=56:28:16, control pressure is 2.5MPa,
Reaction temperature 220～240 DEG C, mixing speed 1000 revs/min, utilize online gas chromatogram after reacting 24 hours
Carry out tail gas composition analysis, calculate reactivity worth.Continue reaction, behind 240 hours and 480 hours
Utilize online gas chromatogram to carry out tail gas composition analysis, calculate reactivity worth.Evaluation result is shown in Table 2 and table 3.
Catalyst performance index includes being catalyzed activity, methane selectively, C5+ selectivity and stability, wherein
Catalysis activity is defined as: the CO that unit interval every gram catalyst converts accounts for total in addition system CO mole
Percent；Methane selectively is defined as: the CO being converted into methane accounts for the mole percent converting CO；
C5+ selectivity is defined as: the CO generating C5+ hydro carbons accounts for the mole percent converting CO；Stability table
Showing that catalyst is catalyzed activity reduction degree after long-time successive reaction, reduce the fewest, stability is the highest,
Otherwise, stability is the poorest.Concrete evaluation result is shown in Table 2 and table 3, relative activity computational methods in table: with
On the basis of the catalysis activity of R-1, the numerical value that the catalysis activity of remaining catalyst obtains by comparison is accordingly
The relative activity of catalyst.
Table 2 catalyst performance evaluation
Table 3 catalyst stability evaluation
It can be seen from the results in table 2 compared with the catalyst that prior art obtains, the present invention provides
Catalyst activity is high, methane selectively is low, C5+ selectivity is high；Result in table 3 shows: the present invention
The catalyst provided has higher stability.
Claims (16)
1. a loaded nano Co catalysts, it is characterised in that by the basis of catalyst and in terms of cobalt element, be catalyzed
In agent, nanometer cobalt content is 3～65 weight %, and the preparation method of described catalyst comprises the steps: (1)
Prepare nano cobalt granule, the nano cobalt granule obtained is scattered in solvent, obtain nanometer cobalt dispersion liquid；(2)
In the nanometer cobalt dispersion liquid that step (1) obtains, it is passed through oxygen-containing gas, obtains one and react with oxygen-containing gas
Nanometer cobalt dispersion liquid；(3) with step (2) obtain dispersion liquid dipping carrier, drying obtains
Loaded nano Co catalysts.
Catalyst the most according to claim 1, it is characterised in that the nanometer cobalt obtained in described step (1)
The particle diameter of grain is 1～20nm；In the dispersion liquid that described step (1) obtains, nanometer cobalt content is 1～10g nanometer
Cobalt/100mL solvent, in described dispersion liquid solvent selected from water, methanol, ethanol, propanol, acetic acid, lactic acid,
One or more in citric acid, Polyethylene Glycol, polyvinylpyrrolidone.
Catalyst the most according to claim 2, it is characterised in that the nano cobalt granule that described step (1) obtains
Particle diameter be 3～15nm；In the dispersion liquid that described step (1) obtains, nanometer cobalt content is 1～5g nanometer cobalt
/ 100mL solvent, one or more in water, methanol, ethanol, propanol of solvent in described dispersion liquid.
Catalyst the most according to claim 1, it is characterised in that the operating condition of described step (2) including:
Temperature-10～60 DEG C, the time is 0.01～24h, on the basis of nanometer cobalt quality, the volume space velocity of oxygen-containing gas
It is 0.2～20L g-1·h-1。
Catalyst the most according to claim 4, it is characterised in that the operating condition of described step (2) including:
Temperature 0～50 DEG C, the time is 0.1～4h, and on the basis of nanometer cobalt quality, the volume space velocity of oxygen-containing gas is
1～10L g-1·h-1。
Catalyst the most according to claim 1, it is characterised in that the oxygen-containing gas in described step (2) is oxygen
Gas and the gaseous mixture of one or more in nitrogen, noble gas, oxygen content in described oxygen-containing gas
For no more than 21 volume %.
Catalyst the most according to claim 6, it is characterised in that in described oxygenous mixed gas, oxygen contains
Amount 0.01～5 volume %.
Catalyst the most according to claim 1, it is characterised in that by the basis of catalyst and in terms of cobalt element,
In catalyst, nanometer cobalt content is 5～50 weight %.
Catalyst the most according to claim 1, it is characterised in that the preparation of step (1) described nano cobalt granule
Method includes: in the presence of protective agent, uses reducing agent that cobalt salt is carried out reduction reaction, obtains nanometer cobalt
Grain, reaction condition includes: reaction temperature is-10～70 DEG C, and the response time is 0.01～4h.
Catalyst the most according to claim 1, it is characterised in that the system of step (1) described nano cobalt granule
Preparation Method includes: cobalt salt and protective agent is joined and obtains cobalt salt in reaction medium and protectant mixing is molten
Liquid, then joins reducing agent in mixed solution and carries out reduction reaction, obtains nano cobalt granule, reacts bar
Part includes: reaction temperature is-10～70 DEG C, and the response time is 0.01～4h, and described reaction medium is water, first
One or more in alcohol, ethanol, propanol, acetic acid, lactic acid, oxolane, citric acid.
11. catalyst according to claim 10, it is characterised in that described reaction medium be water, ethanol, four
Hydrogen furan or its mixture, described reaction condition includes: reaction temperature is 0～40 DEG C, and the response time is
0.1～2h.
12. according to the catalyst described in claim 9 or 10, it is characterised in that described cobalt salt is the inorganic salt of cobalt
Or carboxylate, one or more in sodium borohydride, potassium borohydride, hydrazine hydrate of described reducing agent, institute
State one or more in Polyethylene Glycol, polyvinylpyrrolidone, oleic acid, linoleic acid of protective agent, institute
The ratio stating the reducing agent amount with the material of element cobalt is 3～20:1, the material of described protective agent and element cobalt
The ratio of amount is 10～500:1.
13. catalyst according to claim 12, it is characterised in that the material of described reducing agent and element cobalt
The ratio of amount is 3～15:1, and described protective agent is 20～200:1 with the ratio of the amount of the material of element cobalt.
14. according to the catalyst described in claim 9 or 10, it is characterised in that after obtaining nano cobalt granule,
Also including the step of washing, described washing makes in nano cobalt granule, on the basis of nano cobalt granule weight, to remove
Beyond cobalt, other metallic element weight total content is less than 100ppm, and cleaning solvent therein is selected from water, ethanol
Or its mixture.
Catalyst application in Fischer-Tropsch synthesis described in 15. any one of claim 1～14, including by carbon monoxide
With the mixture of hydrogen and described catalyst haptoreaction, reaction condition is: temperature 160～300 DEG C, pressure
1～8MPa, the mol ratio 0.4～2.5:1 of hydrogen and carbon monoxide, gas volume air speed 200～40000h-1。
16. application according to claim 15, it is characterised in that: described reaction condition includes: temperature
190～280 DEG C, pressure 1～5MPa, the mol ratio 1.0～2.5:1 of hydrogen and carbon monoxide, the volume of gas
Air speed 500～30000h-1。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110284146A (en) * | 2019-06-21 | 2019-09-27 | 青岛科技大学 | Load selenium in situ adulterates molybdenum disulfide/transition metal boride nano material preparation and application |
| CN113617356A (en) * | 2020-05-06 | 2021-11-09 | 中国石油化工股份有限公司 | Cobalt-based catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076402A (en) * | 2004-12-03 | 2007-11-21 | 约翰森·马瑟公开有限公司 | Shaped eggshell catalyst containing cobalt, use and preparation thereof |
| CN102274726A (en) * | 2011-04-29 | 2011-12-14 | 中南民族大学 | Nanoscale cobalt particle Fischer-Tropsch synthetic catalyst and preparation method thereof |
| US20130184360A1 (en) * | 2010-07-22 | 2013-07-18 | Gtl.F1 Ag | Catalyst treatment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076402A (en) * | 2004-12-03 | 2007-11-21 | 约翰森·马瑟公开有限公司 | Shaped eggshell catalyst containing cobalt, use and preparation thereof |
| US20130184360A1 (en) * | 2010-07-22 | 2013-07-18 | Gtl.F1 Ag | Catalyst treatment |
| CN102274726A (en) * | 2011-04-29 | 2011-12-14 | 中南民族大学 | Nanoscale cobalt particle Fischer-Tropsch synthetic catalyst and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110284146A (en) * | 2019-06-21 | 2019-09-27 | 青岛科技大学 | Load selenium in situ adulterates molybdenum disulfide/transition metal boride nano material preparation and application |
| CN113617356A (en) * | 2020-05-06 | 2021-11-09 | 中国石油化工股份有限公司 | Cobalt-based catalyst and preparation method and application thereof |
| CN113617356B (en) * | 2020-05-06 | 2023-10-10 | 中国石油化工股份有限公司 | Cobalt-based catalyst and preparation method and application thereof |
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